Polymers of bisphenols of spirobi



United States Patent 3,388,098 POLYMERS 6F BISPHENOLS 0F SPIROBI(META-DIOXAN) James Harding, Green Brook Township, NJL, assignor tognign Carbide Corporation, a corporation of New lor N 0 Drawing.Original application Apr. 16, 1964, Ser. No. 360,410, new Patent No.3,347,871, dated Get. 17, 1967. Divided and this application Feb. 20,1967, Ser. No. 618,291

12 Claims. (Cl. 260-47) ABSTRACT 0F THE DECLOSURE Polycarbonates,polyurethanes and diglycidyl ethers have been prepared from bisphenolsof spiro'oi(metadioxan) having the formula n having values of 1 to 3, Rbeing H or a lower hydrocarbon radical and Y being halogen, alkyl,alkaryl or aralkyl.

These poly carbonates, polyurethanes and cured diglycidyl ethers. can beused as adhesives, coating and structural elements.

This is a division of Ser. No. 360,410, filed on Apr. 16, 1964, now US.Patent No. 3,347,871, granted Oct. 17, 1967.

This invention relates to novel bisphenols and condensation polymersprepared from them.

Heretofore it has been known to condense phenols with aldehydes andketones to produce bisphenols. The bisphenols thus produced have theirphenolic portions on a single carbon atom. The close proximity of thephenolic portions has limited the control which can be exercised overthe properties of these known bisphenols and condensation polymerscontaining these bisphenol moieties. Methods have been proposed to putthe phenolic portions on different carbon atoms as by a double Friesrearrangement of the phenolic esters of dibasic acids, but suchprocesses have not been practically useful.

It is an object, therefore, of the present invention to providebisphenols wherein the phenolic portions are attached to diiterentcarbon atoms.

It is another object to provide condensation polymers containingbisphenol moieties whose phenolic portions are attached to differentcarbon atoms.

It is another object to provide bisphenol condensation polymers havinghigh glass transition temperatures and inherent toughness.

It is another object to provide bisphenol epoxy resins having high heatdistortion temperatures and tensile properties.

It is another object to provide a practical method for producingbisphenols whose phenolic portions are on different carbon atoms.

It is another object to provide novel bisphenols and bisphenol glycidylethers.

It has now been discovered that bisphenols having phenolic portions onditferent carbon atoms are prepared by contacting togetherpentaerythritol and at least a stoichiometric amount of a carbonylsubstituted phenol with an acidic catalyst.

3,338,098 Patented June 11, 1968 The reaction shown forp-hydroxybenzaldehyde and pentaerythritol proceeds, in general, asfollows:

This compound is a bisphenol of spirobi(meta-dioxan),3,9-bis(p-hydroxyphenyl)spirobi(rneta-dioxan), and is a new compound.

Although a molar excess of carbonyl substituted phenol overpentaerythritol can be employed if desired, a substantiallystoichiometric ratio is preferred, since the isolation of the bisphenolof spirobi(meta-dioxan) is simplified when there is no residual excessof either reactant remaining therewith. Where polysubstitution of thecarbonyl substituted phenol renders it less reactive or slug gish, itmay be desirable to use this component in excess in order to enhance thereaction rate of that particular system but in general, withunsubstituted or less substituted phenolic reactants, a ratio of abouttwo moles of carbonyl substituted phenol to about one mole ofpentaerythritol is especially preferred.

The reaction can be carried out at atmospheric, subatrnospheric, orsuperatmospheric pressure and at temperatures ranging from about 30 C.to about 100 C. Reaction temperatures of about 50 C. to 100 C. permitreaction without the use of elaborate pressure equipment and thus arepreferred. Particularly preferred is reaction under atmospheric pressureat temperatures from C. to C.

Pentaerythritol is a commercially available tetrahydric alcohol meltingat 260 C. which can be prepared by the reaction of acetaldehyde withformaldehyde. It is moderately soluble in cold water, readily soluble inhot water and has a limited solubility in organic liquids.

Phenols which can be reacted with pentaerythritol to form the bisphenolsof this invention are hydroxy substituted aryl compounds having acarbonyl group attached to a ring carbon atom in a position other thanortho, i.e., either meta or para to a phenolic hydroxyl. A carbonylgroup as the term is used in the present specification and claims is amonovalent aldehyde or a ketone radical having the structure wherein Ris hydrogen or a lower hydrocarbon monovalent radical having up to 10carbon atoms. Illustrations of such radicals include those derived fromalkanes, such as, methane, ethane, propane, butane, isobutane, pentane,isopentane, hexane, hcptane, octane, isooctane, Z-ethylhexane, nonane,decane and the like; alicyclics such as cyclobutane, cyclopentane,cyclohexane and the like; and aromatics such as benzene, toluene,xylenes, and the like. Among the phenols deserving of special mentionare: hydroxy substituted benzenes, e.g., phenol, catechol, pyrogallol,resorcinol and trihydroxy substituted benzenes; and substituted phenolshaving in the meta positions, or para position, one or more substituentssuch as alkyl groups, aryl groups, alkaryl groups, aralkyl groups,halogen groups, i.e., fluorine, chlorine, bromine and iodine, alkoxygroups and aryloxy groups. Preferred as substituents in the abovecompounds are straight and branched chain alkyl and aralkyl groupshaving from 1 to 10 carbon atoms, particularly lower alkyl substituents,i.e., having from 1 to 6 carbon atoms. Among the substituted phenolsthose deserving of special mention are the cresols, xylenols, guaiacol,methylphenol, ethylphenol, butylphenol, octylphenol, dodecylphenol,eicosylphenol, tricontylphenol, and tetracontylphenol.

Thus, the term bisphenol of spirobi(meta-dioxan)" used herein includescompounds having the formula wherein R is hydrogen or a lowerhydrocarbon monovalent radical as defined above, Y is a hydrogen,hydroxyl or one or more hydrocarbon substituents free of aliphaticunsaturation, halogen or saturated oxyhydrocarbon substituents on aphenolic ring carbon atom, e.g., selected from alkyl, aryl, alkaryl,aralkyl, alkoxy, hydroxyl r fluorine, chlorine, bromine or iodine groupsand n is an integer from 1 to 3. The point of attachment of the abovephenolic portions can be meta or para to a phenolic hydroxyl.

The catalyst used in the reaction of the above carbonyl substitutedphenols with pentaerythritol in the present invention comprises strongacids as well as the hydrogen form (H of a cation exchanging resin,i.e., an acidic cation exchanging resin.

Representative strong acids which can be used as catalysts in thisinvention include mineral acids such as sulfuric, hydrochloric,hydrofluoric, hydrobrom c, phosphoric, trichloroacetic acids and thelike; acid activated clays such as bentonite; natural and syntheticaluminosilicates such as Linde decationized molecular sieves orzeolites; and arylsulfonic acids such as p-toluenesulfonic,benzenesulfonic, benzene-m-disulfonic, benzene-p-disulfonic acids andthe like. The concentration of acid catalyst is not narrowly criticalwith as little as 0.05 parts and as much as parts per hundred ofpentaerythritol being equally effective. A preferred range lies betweenabout 0.1 and 3.0 parts of acid per hundred parts of pentaerythritolbeing equally effective. A preferred range lies between about 0.1 and3.0 parts of acid per hundred parts of pentaerythritol.

The cation exchanging resins are insoluble in the reaction mixture andhence, there is no problem of catalyst separation from the reactionmixture or need of removal of small amounts of catalyst residues in theproduct. The service life of the acidic cation exchanging resin in thismethod is nearly infinite and hence, the resin does not of necessityhave to be regenerated, if care is exercised in preventing theintroduction of basic metal ions such as sodium, potassium, calcium,etc. or other contaminants which inactivate the cation exchanging groupsof the resin. The use of this insoluble catalyst confers the additionaladvantagse of 1) eliminating the need for acid corrosion resistantequipment which is otherwise esse tial, and (2) making unnecessary anyneutralization steps.

The cation exchanging resins are substantially insoluble polymericskeletons with strongly acidic cation exchanging groups chemically boundthereto. The exchange potential of the bound acidic groups and thenumber of them which are available for contact with the reaction mixturedetermine the catalytic effectiveness of a particular cation exchangingresin. Thus, although the number of acidic groups bound to the polymericskeleton of the resin determines the theoretical exchange capacitythereof, a more accurate criterion of catalytic effectiveness is thenumber of acidic groups available for contact with the reactants. Thiscontact can occur on the surface or in the interior of the cationexchanging resin; therefore, a physical form of resin which provides amaximum amount of surface area for contact and diffusion, e.g., porousmicrospheres or beads, is highly desirable and affords the highest rateof reaction and reaction economy in this process. The particular form ofthe cation exchanging resin used, however, is not critical.

The cation exchanging resins should be substantially insoluble in thereaction mixture and in any solvent to which the resin may be exposed inservice. Resin insolubility is generally attributable to crosslinkingwithin the resin but can be caused by other factors, e.g., highmolecular weight or a high degree of crystallinity.

In general, the greater the exchange capacity of a resin, i.e., thegreater the number of milliequivalents of acid per gram of dry resin,the more desirable is the resin. Resins having an exchange capacitygreater than about two milliequivalents of acid per gram of dry resinare preferred. Particularly preferred are resins with bound cationexchanging groups of the stronger exchange potential acids. Resultsobtained with cation exchanging resins having bound sulfonic acid groupshave been highly satisfactory. Among the cation exchanging resins whichare highly deserving of special mention are: sulfonatedstyrene-divinylbenzene copolymers, sulfonated crosslinked styrenepolymers, phenol-formaldehyde sulfonic acid resins, benzene formaldehydesulfonic acid resins, and the like. Most of these resins and many othersare available commercially under trade names such as: Amberlite XE-IOO.(Rohm and Haas Co.); Dowex 5O X-4 (Dow Chemical Co.); Permutit QH(Permutit Co.); and Chempro C-ZO (Chemical Process C0.).

Many cation exchanging resins are received from the manufacturer in theform of the sodium or other salt and must be converted to the hydrogenor acid form prior to use in this process. The conversion can be easilyaccomplished by washing the resin with a solution of a suitable mineralacid, e.g., sulfuric, hydrofluoric or hydrochloric acids. For example, asulfonated resin can be suitably washed with a sulfuric acid solution.Salts formed during the conversion procedure are conveniently removed bywashing the resin with water or solvent for the salt.

It frequently happens as a result of either the washing operationoutlined above, or the manufacturers method of shipping, that the resinWill contain from 50 percent to percent of its own weight of water. Allbut about 2% of this water as a maximum is preferably removed prior touse of the cation exchanging resin. Suitable methods for removing thewater in the resin include drying the resin under reduced pressure in anoven; soaking the resin in a melted anhydrous phenol for a timesufiicient to fill the resin interspaces with a phenol; and azeotropicdistillation of the water.

The resin when once conditioned in this manner, to insure anhydrousconditions, i.e., 2% water throughout, does not require reconditioningat any time during use. Alternatively, the resin can be conditionedafter installation in the process equipment merely by running thereaction mixture through the resin until sufficient water is removed. Inthis latter procedure dehydration is accomplished by the reactionsolvent.

Solvents are not essential for this invention, but their use ispreferred. Solvents which can be employed in preparing the bisphenols ofthis invention include aromatics, such as benzene, toluene, xylene andthe like, alicyclics such as cyclohexane, methylcyclohexane and the likeand polar solvents such as dimethyl sulfoxide, dimethyl formamide,nitroethane, and the like. While the choice of solvent is not critical,the synthesis of the bisphenols of pentaerythritol is more efiicientwhen a solvent system is established in which both pentaerythritol andthe starting phenol are soluble. In this regard a mixture of a polarsolvent such as dimethyl sulfoxide and an aromatic solvent such asbenzene is particularly preferred. This mixture provides an azeotropingsolvent which can serve to remove water formed during the reaction aswell as water present in the cation exchanging resins if such are usedas the catalyst.

The product bisphenols in solution are readily separable from the resincatalyst by filtration and can be purified by a vacuum strippingoperation which removes undesirable impurities.

Polypentaerythritols such as dipentaerythritol, tripentaerythritol andtetrapentaerythritol as well as cyclic polyhydroxyalcohols as forexample anhydroenneahepitol,

2,3,5,6 tetramethylol 1,4 hydroquinone dimethyl ether and the like cansubstituted for pentaerythritol in this invention if so desired.

It has been found that a variety of useful polymers can be synthesizedfrom the bisphenols of this invention. For example, by reacting thesebisphenols with epihalohydrins, epoxy resins are produced which whenhardened with curing agents, well known in the art, afford thermosetresins having high heat distortion temperature, as well as high tensile,impact, and flexural strengths. In a typical synthesis 3,9 bis(phydroxyphenyl)spirobi(metadioxan) and an epihalohydrin afford the epoxyresin or glycidyl ether shown below:

Various epihalohydrins such as epichlorohydrin, epibromohydrin,epiiodohydrin, and substituted epihalohytetrachloroethane and aliphaticalcohols, e.g., methanol, ethanol, isopropanol and the like. It ispreferred to use ethanol as the solvent in the practice of thisinvention.

The quantities of bisphenol and epihalohydrin should be such that atleast two moles of epihalohydrin are present for each mole of bisphenol.The diluent concentration can be varied to give concentrations of fromabout 5% to 90% solids. The catalyst concentration generally rangesbetween 0.01% and 5% by weight based on the bis-phenol. The reactiontemperature usually ranges between C. and 190 C. as determined by thediluent used, and the pressure. Pressures above atmospheric are notnecessary but can be employed if desired, as can less than atmosphericpressures. The reaction time required for the formation of thediglycidyl ethers of this invention will vary with the reactiontemperature used but ordinarily a range from 2 to 30 hours can be used.

The conversion of the diglycidyl ethers of3,9-bis(p-hydroxyphenyl)spirobi(meta-dioxan) to thermoset resins may beeffected by methods well known in the epoxy resin curing art, thusfacilitating their use with conventional equipment presently employed byfabricators using epoxy resins. These diglycidyl ethers may be cured orhardened by reaction with organic acids, organic acid anhydrides, andprimary, secondary and tertiary amines, preferably in approximatelystoichiometric amounts. Examples of suitable curing agents includeoxalic acid, phthalic anhydride, hexahydrophthalic anhydride,pyromellitic anhydride, chlorendic anhydride, maleic anhydride, ethylenediamine, diethylene triamine, triethylene tetramine, dimethylamine,propylamine, boron trifiuoride monoethylarnine complexes, hydroxyethyldiethylene triamine, piperidene, umethylbenzyl dimethylamine,tridimethylarninomethyh phenol, meta-phenylene diamine and the like. Thecuring conditions, viz, proportions of reactants, curing time and curingtemperature depend on the curing agent used. In general, curing times of5 minutes to 4 days and temperatures from 25 C. to 250 C. are employed.Room temperature cures in 3 to 6 hours may be achieved withpolyfunctional amines while carboxylic acid cures require temperaturesof 100 to 150 C. for complete reaction in 3 to 6 hours.

The general formula of the diglycidyl ethers available from thebisphenols of this invention is shown below:

wherein R is hydrogen or a lower hydrocarbon radical, Y is hydrogen,halogen or a lower hydrocarbon radical and a is an integer having valuesof 0 to 2 Another class of useful polymers that can be prepared from thebisphenols of spirobi(meta-dioxan) is the polycarbonates by means of aninterfacial condensation system. In a preferred synthesis thedichloroformate of the bisphenol of spirobi(meta-dioxan) is preparedfirst with phosgene and dimethyl aniline. When polymerized with anaqueous sodium hydroxidemethylene chloride mixture, a polycarbonate isobtained represented by the structure:

0--CH CH O 0 2 C-R C R- CO CH 0 Y wherein x is an integer having a valuesufficiently high as to afford a normally solid polymer, R is hydrogenor a lower hydrocarbon radical as previously defined and a is a is aninteger having values of 0 to 2. I

The preparation of these polycarbonates is not limited to this methodsince direct phosgenation or ester interchange utilizing a diarylcarbonate, such as diphenyl carbonate, can also be employed.

Another series of useful condensation polymers available from thebisphenols of spirobi(meta-dioxan) is the polyurethanes. Thus, when thedichloroformate of a bisphenol of spirobi(meta-dioxan) is caused toreactwith piperazine a polyurethane is obtained having the structure whereinx is an integer having values sufliciently high as to afford a normallysolid polymer, Y, R and a are as defined above for the polycarbonates.

Polyesters of bisphenols of spirobi(meta-dioxan) can be synthesized byinteracting dicarboxylic acids, esters or acid halides with bisphenolsof spirobi(meta-dioxan), with or without the use of a solvent.

Poly(hydroxyethers) of bisphenols of spirobi(metadioxan) can be preparedby the procedure described in French Patent 1,309,491.

Other applications for the bisphenols of spirobi(metadioxan) includetheir use as hardeners for epoxy resins, bacteriocides, fungicides,miticides and antioxidants.

The following examples illustrate the practice of the present invention.All parts and percentages are by weight unless otherwise stated.

Example l.Preparation of 3,9-bis(p-hydroxyphenyl) spirobi(meta-dioxan) Aliter, threeneck, round-bottom fiask equipped with a mechanicalagitator, condenser, Dean-Stark moisture trap and thermometer wascharged with 800 g. of dimethyl sulfoxide, 1000 g. of benzene and 144 g.of Dowex 50 X-4 cation exchanging resin (a sulfonated styrene-divinylbenzene copolymer) followed by refluxing for 9.5 hours at a temperatureof about 92-94 C. The water which had collected in the Dean-Stark trapwas discarded. Then 150 g. (7.1 moles) of mono-pentaerythriotol and 275g. (2.25 moles) of p-hydroxybenzaldehyde was added to the reactionflask. The reactants were left at reflux temperature, for an additional15 hours during which period about 44 g. of aqueous distillate wascollected in the Dean-Stark trap. theorectically 2.2 moles ofp-hydroxybenzaldehyde should produce 39.6 g. of water in this reaction.The Dowex cation exchanging resin was separated from the reactants byfiltration for re-use in further reactions. The hot filtrate was dilutedwith 2000 ml. of benzene and cooled whereupon 347 g. (92% yield of3,9-bis(p-hydroxyphenyl)- spirobi(meta-dioxan) crystallized out ofsolution. This product was isolated by filtration, washed with anadditional 2000 ml. of benzene and dried. It then was found to have amelting range of 249-257 C. and an hydroxyl content of 10.0%(theoretical-9.9%).

Example 2.Preparation of 3,9-bis(p-chlorohydroxyphenyl)spirobi(meta-dioxan) The procedure described inExample 1 is followed with 352 g. (2.25 moles) of3-chloro-4-hydroxybenzaldehyde being substituted for thep-hydroxybenzaldehyde and affords 3,9-bis(p 2chlorohydroxyphenyl)spirobi(metadioxan).

Example 3.Preparation of3,9-bis(p-2-methy1hydroxyphenyl)spirobi(meta-dioxan) The proceduredescribed in Example 1 is followed with 333 g. (2.25 moles) of3-methyl-4-hydroxybenzaldehyde being substituted for thep-hydroxybenzaldehyde and atfords 3,9-bis(p 2methylhydroxyphenyl)spirobi(metadioxan).

Example 4.Epoxidation of 3,9-bis(p-hydroxyphenyl) spirobi(meta-dioxan) A3-neck, 3 liter round-bottom flask equipped with a reflux condenser,thermometer, mechanical agitator, and dropping tunnel was charged with1110 g. (12.0 moles) of epicholorohydrin, 344 g. of ethanol and 688 g.(2.0 moles) of 3,9-bis(p-hydroxyphenyl)spirobi(meta-dioxan). Dissolutionof the reactants was achieved by heating the ....O 9 1 a .& cn rmreactants to 60 C. Then 184 g. of 50% aqueous sodium hydroxide was addedwith stirring at 60-65 C. according to the schedule below:

Grams Over a 1 hour period 18.4 During the next 30 minutes 18.4 Duringthe following hour 128.8 During the last hour 18.4

Stirring was continued for an additional 20 minutes and then excessunreacted epicholorohydrin and ethanol removed by distillation undervacuum. The viscosity of the residual slurry was reduced by the additionof 900 g. of methyl isobutyl ketone and a series of washings wereinitiated with 500 ml. portions of water in the separatory funnel. Thewashings were continued until the pH was less than 8. The organic layerwas vacuum distilled until a residue consisting of a white filter-ableslurry remained. The diglycidyl ether of3,9-bis(p-hydroxyphenyl)spirobi- (meta-dioxan) was obtained byfiltration of the slurry. After drying this product had a melting pointof 158 C., an epoxy assay of 242 (theoretical 228) and weighed 608 g.(66% yield).

Example 5.Epoxidation of3,9-bis(p-Z-methylhydroxyphenyl)spirobi(rneta-dioxan) The proceduredescribed in Example 4 is followed with 718 g. (2 moles) of3,9-bis(p-2-methylhydroxyphenyl)- spirobi(meta-dioxan) being substitutedfor the 3,9-bis(phydroxyphenyl)spirobi(meta-dioxan) and affords thediglycidyl ether of 3,9-bis(p-2-methylhydroxyphenyl)spirobi(meta-dioxan)Example 6.Epoxidation of3,9-bis(p-Z-chlorohydroxyphenyl)spirobi(meta-dioxan) The proceduredescribed in Example 4 is followed with 759 g. (2 moles) of3,9-bis(p-2-chlorohydroxyphenyl)- spirobi(meta-dioxan) being substitutedfor the 3,9-bis,phydroxyphenyl)spirobi(meta-dioxan) and aifords thediglycidyl ether of3,9-bis(p-2-chlorohydroxyphenyl)spirobi(meta-dioxan).

Example 7.-Curing of diglycidyl ether of3,9-bis(p-hydroxy)spirobi(meta-dioxan) Izod impact strength (ASTMD-256-56) ft./lbs./in 0.60 Heat distortion temperature (ASTM D-648- 56)C- 181 Tensile strength (ASTM D-63858T) -..p.s.i 9,300 Elongation (ASTMD-638-58T percent 3.6 Modulus of elasticity (ASTM D-638-58T p.s.i352,000 Flexural strength (ASTM D-790-58T) p.s.i 18, 340

Flexural modulus (ASTM D-79058T) p.s.i 552,200

The epoxy resins of this invention can be used for pottmg compounds,adhesives, coating applications and as a heat resisting encapsulationmedium.

Example 8.-Preparation of the dichloroformate of 3,9-bis(p-hydroxyphenyl)spirobi(meta-dioxan) To a slurry of 34.5 g. (0.1mole) of 3,9-bis(p-hydroxyphenyl) spirobi(meta-dioxan) and 250 ml. ofdry toluene cooled to C. and contained in a one liter, B-neck,round-bottom flask equipped with a mechanical stirrer, reflux condenser,thermometer and dropping funnel is added 19.8 g. (0.2 mole) of phosgene.A solution of 24.2 g. (0.2 mole) of N,N-dimethylaniline in ml. of drytoluene is then added dropwise from the dropping funnel. The reactionmixture is stirred at ambient temperatures for about 2 hours. Insolubledimethylaniline hydrochloride is removed from the reaction product byfiltration and the filtrate stripped of solvent in a vacuumdistillation. The residue is dissolved in 100 ml. of methylene chlorideand the solution passed through a silica gel column (12" high and 1% indiameter). The product is eluted with 600 ml. of methylene chloride andthe combined eluants are stripped free of solvent. The residue is thedichloroformate of 3,9-bis(p-hydroxyphenyl)spirobi- (meta-dioxan)Example 9.-Preparation of the dichloroformate of 3,9-bis(p-Z-chlorohydroxyphenyl)spirobi(meta-dioxan) The procedure describedin Example 8 is followed with 41.4 g. (0.1 mole) of3,9-bis(p-2-chlorohydroxyphenyl)- spirobi(meta-dioxan) thus affordingthe dichloroformate of 3,9-bis (p-2chlorohydroxyphenyl)spirobi(meta-diox- Example 10.-Preparation of thedichloroformate of 3,9- bis(p-2-methylhydroxyphenyl)spirobi(meta-dioxan) The procedure described inExample 8 is followed using 37.3 g. (0.1 mole) of3,9-bis(p-Z-methylhydroxyphenyl)- spirobi(meta-dioxan) as the bisphenolreactant. In this manner the corresponding dichloroformate is obtained.

Example 11.Polymerization of the dichloroformate of3,9-bis(p-hydroxyphenyl)spirobi(meta-dioxan) A solution of 4.58 g. (0.01mole) of the dichloroformate of 3,9-bis(p-hydroxyphenyl)spirobi(metadioxan) in ml. of methylene chloride is added to a solution of 1.0 g. ofsodium hydroxide in 50 ml. of water, 3 drops of triethylamine and 0.014g. of phenol contained in a 3-neck Morton flask, equipped with amechanical stirrer, reflux condenser and thermometer. The reactionmixture is stirred for ten minutes. The organic layer is then washedwith three 200 ml. portions of water by stirring in the Morton flask for10 minutes. The organic layer is washed with successive portions ofwater until a pH of about 6 is attained. The organic layer is thenslowly poured into a Waring Blendor containing 250 ml. of isopropanol.The polycarbonate of 3,9-bis(p-hydroxyphenyl)spirobi(metadioxan) is thenprecipitated and its structure may be represented as shown below:

wherein x is an integer having a value sufficiently high to afford anormally solid polymer.

Example 12.Polymerization of the dichloroformate of3,9-bis(p-2-chlorohydroxyphenyl)spirobi(meta-dioxan) The proceduredescribed in Example 11 is followed with 5.27 g. (0.1 mole) of thedichloroformate of 3,9- bis(p-2 chlorohydroxyphenyl)spirobi(meta-dioxan)substituted for the dichloroformate of3,9-bis(p-hydroxyphenyl)spirobi(metadioxan) and affords thecorresponding polycarbonate.

Example 13.-Preparation of the dichloroformate of 3,9- bis(p-2-methylhydroxyphenyl spirobi (meta-dioxan) The procedure describedin Example 11 is followed with 4.86 g. (0.1 mole) of the dichloroformateof 3,9bis- (p-Z-methylhydroxyphenyl)spirobi(meta-dioxan) and affords thecorresponding polycarbonate.

The polycarbonate of this invention can be used for the fabrication ofelectrical switch components and connectors, instrument cases, lenses,water pump impellers and the like. Extruded film of these polycarbonatescan be employed for capacitors and packaging.

Example l4.Polyurethane of 3,9-bis(p-hydroxyphenyl)spir0bi(meta-dioxan)A solution of 0.86 g. (0.01 mole) of piperazine, 1.0 g. (0.025 mole) ofsodium hydroxide, 0. 01 g. of phenol and 0.1 ml. of triethylamine in 50ml. of water is charged to the reaction vessel described in Example 5. Asolution of 4.57 g. (0.01 mole) of the dichloroformate of3,9-bis(p-hydroxyphenyl)spirobi(meta-dioxan) in 50 ml. of methylenechloride is added with stirring. After 5 minutes of stirring the aqueouslayer is decanted. The organic layer is washed with water and thenpoured into a Waring Blendor containing 300 ml. of isopropanol toprecipitate the polyurethane of 3,9-bis(p-hydroxyphenyl) s pirobi(meta-dioxan The structure of this polyurethane may be represented asshown below:

wherein x is an integer having values sufiiciently high to afford anormally solid polymer.

The polyurethanes of this invention can be used to provide tough,abrasion resistant finishes on floors, wire, leather and rubber goodsand the like.

Example 15.Polyurethane of 3,9-bis(p-2-methylhydroxyphenol) spirobi(meta-dioxan) The procedure and apparatus of Example 14 are used with5.74 g. (0.01 mole) of3,9-bis(p-2-methylhydroxyphenyl)spirobi(meta-dioxan). The polyurethaneof 3,9- bis(p 2 methylhydroxyphenyl)spirobi(meta-dioxan) which forms issimilar in physical properties to that derived from 3,9 bis(phydroxyphenyl)spirobi(metadioxan).

Although the invention has been described in its preferred forms, it isunderstood that the present disclosure has been made only by way ofexample, and that numerous changes in the details may be resorted towithout departing from the spirit and scope of the invention.

What is claimed is:

1. The bisphenol of spirobi(meta-doxan)polycarbonate having thestructure wherein Y is a member selected from the group consisting ofhydrogen, chlorine and methyl.

2. The polycarbonate claimed in claim 1 wherein Y is hydrogen.

3. The polycarbonate claimed in claim 1 wherein Y is methyl.

4. The polycarbonate claimed in claim 1 wherein Y is chlorine.

3,388,098 Ill 12 '5. The bisphenol of spirobi(meta-dioxan) polyurethanehaving the structure:

wherein Y is a member selected from the group consisting 10 of hydrogen,chlorine and methyl. 11. The diglicidyl ether claimed in claim 7hardened 6. The polyurethane claimed. in claim 5 wherein Y with a curingamount of a curing agent. is hydrogen. 12. The hardened diglycidyl etherclaimed in claim 7 7. The diglycidyl ether of a bisphenol ofspirobi(metawherein the curing agent is a polyamine. dioxan) having thestructure 5 O-CH: CHz-O wherein Y is a member selected from the groupconsisting References cued of hydrogen, chlorine and methyl. 25 UNITEDSTATES PATENTS 8. The diglycidyl ether claimed in claim 7 wherein Y 3123 255 4/1964 M G t 1, 260 47 is hydrogen. 3,161,619 12/1964 Rice eta1. 260-78 9. The diglycidyl ether claimed in claim 7 wherein 3,24 ,0114/1966 Muller et a1. 260-340.7 Y is m hy 3,287,32O 11/1966 Leech et al.260-75 10. The diglycidyl ether claimed in claim 7 wherein 30 Y ischlorine. SAMUEL H. BLECH, Primary Examiner.

